2222-33-5

Basic information

• Product Name: 5-Dibenzosuberenone
• Synonyms: 5H-DIBENZO[A,D]CYCLOHEPTEN-5-ONE;5H-DIBENZO(A,D)CYCLOHEPTENE-5-OL;5-DIBENZOSUBERENONE;Dibenzosuberenone,97%;Dibenzo[a,d]cyclohepten-5-one;NSC 86151;Cyclobenzaprine Dibenzosuberenone IMpurity;Cyproheptadine IMpurity B (Dibenzosuberenone)
• CAS NO: 2222-33-5
• Molecular Formula: C₁₅H₁₀O
• Molecular Weight: 206.24
• EINECS: 218-737-3
• Product Categories: API intermediates;intermediate of cyclobenzaprine, cyproheptadine, d;Others chemical reagents;Aromatics;Intermediates;Pharmaceutical Intermediates
• Mol File: 2222-33-5.mol
• Article Data: 39

Chemical Properties

• Melting Point: 87-88 °C(lit.)
• Boiling Point: 210 °C / 3mmHg
• Flash Point: 160.2 °C
• Appearance: White to pale yellow or beige/Crystalline Powder
• Density: 1.0701 (rough estimate)
• Vapor Pressure: 1.75E-05mmHg at 25°C
• Refractive Index: 1.6324 (estimate)
• Storage Temp.: Refrigerator
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly)
• Water Solubility: Soluble in chloroform, ethyl acetate. Insoluble in water.
• BRN: 743171
• CAS DataBase Reference: 5-Dibenzosuberenone(CAS DataBase Reference)
• NIST Chemistry Reference: 5-Dibenzosuberenone(2222-33-5)
• EPA Substance Registry System: 5-Dibenzosuberenone(2222-33-5)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 24/25-36-26
• RIDADR: 3077
• WGK Germany: 3
• RTECS: HP1147500
• TSCA: Yes
• HazardClass: 9
• PackingGroup: III
• Hazardous Substances Data: 2222-33-5(Hazardous Substances Data)

Usage

Chemical Properties

5-Dibenzosuberenone is white to pale yellow or beige crystalline powder

Uses

5-Dibenzosuberenone Can be used in the synthesis of a series of potent antidepressants.

Synthesis Reference(s)

Journal of Medicinal Chemistry, 8, p. 886, 1965 DOI: 10.1021/jm00330a044

InChI:InChI=1/C15H10O/c16-15-13-7-3-1-5-11(13)9-10-12-6-2-4-8-14(12)15/h1-10H

Synthetic route

trans-10,11-dibromo-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (39654-52-9) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With sodium selenite; rac-cysteine In tetrahydrofuran; water at 0℃; for 0.0833333h;	99%
With dimethyl sulfoxide at 75℃; for 2h;	98%
With hydrogenchloride; samarium In tetrahydrofuran for 0.166667h; Ambient temperature;	96%

10,11-dibromo[(10,11-dihydro-5H-dibenzo[a,d]cyclohept-5-one)] (57295-97-3) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With N,N,N,N,-tetramethylethylenediamine; sexithiophene In N,N-dimethyl-formamide for 1h; Inert atmosphere; Irradiation;	99%
With sodium hydride; 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane hydro-chloride In [D3]acetonitrile for 2h;	92%

5H-dibenzo[a,d]cyclohepten-5-ol (10354-00-4) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With Merrifield's resin-bound N-aminoimidazolium chlorochromate In dichloromethane for 2.5h; Heating;	95%
With tert.-butylhydroperoxide In water at 100℃; for 24h;	91%
Stage #1: 5H-dibenzo[a,d]cyclohepten-5-ol With 7,7-dichlorocyclohepta-1,3,5-triene In dichloromethane; dimethyl sulfoxide at -30℃; for 0.333333h; Swern Oxidation; Inert atmosphere; Stage #2: With triethylamine In dichloromethane; dimethyl sulfoxide at -30 - 20℃; for 0.333333h; Swern Oxidation; Inert atmosphere;	88%

trans-10,11-dibromodibenzosuberenone (39654-52-9, 57295-97-3, 123835-95-0) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With indium; niobium pentachloride In tetrahydrofuran at 20℃; for 0.166667h; Sonication; chemoselective reaction;	95%
With indium; cobalt(II) chloride hexahydrate In methanol at 20℃; for 1h;	94%
With gallium; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.416667h; Inert atmosphere; Ultrasonic irradiation; chemoselective reaction;	92%

5,5-dimethoxy-5H-dibenzocycloheptene (1087-68-9) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With dimethylboron bromide In dichloromethane; 1,2-dichloro-ethane at -78℃; for 1h;	93%
With dimethylboron bromide; sodium hydrogencarbonate 1) CH2Cl2, -78 deg C, 1h, 2) THF, 5 min; Yield given. Multistep reaction;

5-(3,3-diphenyl-2,3-dihydro-2-oxoindol-1-yl)dibenzocyclohepten-1-yl diphenylethanoate (101023-29-4) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With hydrogenchloride; water In acetic acid for 1h; Heating;	83%

10,11-epoxy-10,11-dihydrodibenzo[a,d]cyclohepten-5-one (4444-44-4) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With indium; indium chloride In water; tert-butyl alcohol at 84℃; for 6h;	81%

5-Allyl-dibenzo-cyclohepten-5-ol (16203-85-3) → C19H18O + 9.18-Dioxo-4b.4c.9.13b.13c.18-hexahydro-tetrabenzocyclobutadicyclohepten (17044-52-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
In ethyl acetate at 20℃; for 2h; Inert atmosphere; Photolysis;	A 81% B 6% C 8%

5-phenyl-5H-dibenzocyclohepten-5-ol (55090-29-4) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With sulfuric acid; dihydrogen peroxide; acetic acid for 4h; Ambient temperature;	79%

5-<(5H-dibenzocyclohepten-5-yl)oxy>-5H-dibenzocycloheptene (35066-77-4) → suberene (256-81-5) + dibenzosuberenon (2222-33-5)

Conditions	Yield
With iodine In neat (no solvent) at 85℃;	A 73% B 79%

10,11-Dihydro-5H-dibenzo[a,d]cyclohepten-5-one (1210-35-1) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With bromine at 140℃;	70%
With tetrachloromethane; N-Bromosuccinimide; dibenzoyl peroxide Erhitzen des Reaktionsprodukts mit Triaethylamin;
With tetrachloromethane; N-Bromosuccinimide; dibenzoyl peroxide Erhitzen des Reaktionsprodukts mit Pyridin;

5-Allyl-dibenzo-cyclohepten-5-ol (16203-85-3) → C19H18O + dibenzosuberenon (2222-33-5)

Conditions	Yield
In ethyl acetate at 20℃; for 2h; Inert atmosphere; Photolysis;	A 68% B 25%

5-(3,3-dimethyl-2,3-dihydro-2-oxoindol-1-yl)dibenzocyclohepten-1-yl 2-methylpropanoate (101023-28-3) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With hydrogenchloride; water In acetic acid for 0.5h; Heating;	51%

C34H28O2 → 9.18-Dioxo-4b.4c.9.13b.13c.18-hexahydro-tetrabenzocyclobutadicyclohepten (17044-52-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
In ethyl acetate at 20℃; for 2h; Solvent; Inert atmosphere; Photolysis;	A 12% B 50%

dibenzosuberol (1210-34-0) → suberene (256-81-5) + anthracene (120-12-7) + 9-methylanthracene (779-02-2) + dibenzosuberenon (2222-33-5)

Conditions	Yield
With quartz at 350 - 650℃; Inert atmosphere; Pyrolysis;	A 20% B 15% C 12% D 40%

C34H28O2 → 5,5'-bi(5H-dibenzocycloheptenyl) (15224-49-4) + C30H22 + 9.18-Dioxo-4b.4c.9.13b.13c.18-hexahydro-tetrabenzocyclobutadicyclohepten (17044-52-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
In ethyl acetate at 20℃; for 2h; Solvent; Inert atmosphere; Photolysis;	A 8% B 6% C 22% D 39%
In ethyl acetate at 20℃; for 2h; Inert atmosphere; Photolysis;	A 14% B 8% C 38% D 20%

5-diazo-5H-dibenzocycloheptene (6141-56-6) → suberene (256-81-5) + 4H-Cyclopenta[def]phenanthrene (203-64-5) + dibenzosuberenon (2222-33-5)

Conditions	Yield
at 450℃; under 1E-05 Torr;	A n/a B 17% C n/a
at 450℃; under 1E-05 Torr; Mechanism;	A n/a B 17% C n/a

suberene (256-81-5) → dibenzosuberenon (2222-33-5)

Conditions	Yield
With 1,4-dioxane; selenium(IV) oxide

cis-stilbene-2-carbonyl chloride → dibenzosuberenon (2222-33-5)

Conditions	Yield
With aluminium trichloride

methanol (67-56-1) + 5-diazo-5H-dibenzocycloheptene (6141-56-6) → 5-methoxy-5H-dibenzocycloheptene (55789-73-6) + 5,5-dimethoxy-5H-dibenzocycloheptene (1087-68-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
at 60℃; electrooxidation;	A 56.6 % Spectr. B 30.2 % Spectr. C 7.1 % Spectr.
at 60℃; electrooxidation;	A n/a B 30.2 % Spectr. C n/a

methanol (67-56-1) + C15H10N2(1+) (109217-78-9) → 5-methoxy-5H-dibenzocycloheptene (55789-73-6) + 5,5-dimethoxy-5H-dibenzocycloheptene (1087-68-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
With tetramethylammonium tetrafluoroborate In acetonitrile at 0 - 50℃; Kinetics; Thermodynamic data; electrolyte effect, substrate concentration, effect of solvent, deuterated solvent (in methanol), ΔH(excit.), ΔS(excit.);

5-diazo-5H-dibenzocycloheptene (6141-56-6) → 5-methoxy-5H-dibenzocycloheptene (55789-73-6) + 5,5-dimethoxy-5H-dibenzocycloheptene (1087-68-9) + dibenzosuberenon (2222-33-5)

Conditions	Yield
In methanol at 60℃; electrooxidation;	A 56.6 % Spectr. B 30.2 % Spectr. C 7.1 % Spectr.

(10S,11S)-10,11-Dichloro-10,11-dihydro-dibenzo[a,d]cyclohepten-5-one → dibenzosuberenon (2222-33-5)

Conditions	Yield
With 1,5-diselenacyclooctane In chloroform at 90℃; for 95h;	28 % Chromat.

5H-6,7-dihydrodibenzo[a,c]cyclohepten-6-ol (3594-99-8) → suberene (256-81-5) + anthracene (120-12-7) + 9-methylanthracene (779-02-2) + dibenzosuberenon (2222-33-5)

Conditions	Yield
at 350℃; under 997.58 Torr; Product distribution; Further Variations:; Temperatures; other dibenzocycloalkanols;	A 15 % Spectr. B 4 % Spectr. C 4 % Spectr. D 20 % Spectr.

dibenzosuberane (833-48-7) → 10,11-Dihydro-5H-dibenzo[a,d]cyclohepten-5-one (1210-35-1) + dibenzosuberenon (2222-33-5)

Conditions	Yield
With aluminum oxide; Ru(OH)x; oxygen In 1,2-dichloro-benzene at 169.85℃; under 760 Torr; for 5h;

5H-dibenzocyclohepten-5-one hydrazone (61047-37-8) → dibenzosuberenon (2222-33-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) sodium sulphate, yellow mercuric oxide, potassium hydroxide, Celite / 1.) diethyl ether, ethanol, 3 h, 2.) ethanol, diethyl ether, room temp., overnight 2: 82 percent / benzene / 8 h / Ambient temperature 3: 83 percent / water, hydrochloric acid / acetic acid / 1 h / Heating View Scheme

dibenzocyclohepten-5-ylidene(phenyl)amine N-oxide (101023-27-2) → dibenzosuberenon (2222-33-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 82 percent / benzene / 8 h / Ambient temperature 2: 83 percent / water, hydrochloric acid / acetic acid / 1 h / Heating View Scheme

o-phenethylbenzoic acid (4890-85-1) → dibenzosuberenon (2222-33-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: polyphosphoric acid 2: bromine / Irradiation View Scheme

diphenylethane-2-carboxylic acid chloride (36795-27-4) → dibenzosuberenon (2222-33-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: AlCl3; CS2 2: N-bromo-succinimide; CCl4; dibenzoyl peroxide / Erhitzen des Reaktionsprodukts mit Triaethylamin View Scheme

dibenzosuberenon (2222-33-5) → dibenzosuberane (833-48-7)

Conditions	Yield
With iodine; hypophosphorous acid In acetic acid for 72h; Reduction; Heating;	100%
With potassium hydroxide; Raney Ni-Al alloy In water at 90℃; for 8h;	92%
With ethanol; platinum Hydrogenation;
With ethanol; sodium

methylamine (74-89-5) + dibenzosuberenon (2222-33-5) → N-methyl-5H-dibenzocyclohepten-5-imine (59864-52-7)

Conditions	Yield
With titanium tetrachloride In toluene at -10 - 20℃; Inert atmosphere;	100%
With titanium tetrachloride In benzene for 144h; Ambient temperature;	95%
With titanium tetrachloride In toluene

dibenzosuberenon (2222-33-5) → N-[tricyclo[9.4.0.03,8]pentadeca-1(11),3,5,7,9,12,14-heptaen-2-ylidene]hydroxylamine (1021-91-6)

Conditions	Yield
With hydroxylamine hydrochloride In pyridine for 20h; Reflux; Inert atmosphere;	100%
With pyridine; hydroxylamine hydrochloride for 15.5h; Reflux;	100%
With pyridine; hydroxylamine hydrochloride In ethanol Reflux;	98%

dibenzosuberenon (2222-33-5) → suberene (256-81-5)

Conditions	Yield
With lithium aluminium tetrahydride; aluminium trichloride In tetrahydrofuran; diethyl ether	99%
With lithium aluminium tetrahydride; aluminium trichloride In diethyl ether	65%
With aluminum isopropoxide at 250℃; for 0.166667h;	50%
With potassium hydroxide; hydrazine hydrate; isopropyl alcohol Reagens 4: Propan-1,3-dion; Abdestillieren des Loesungsmittels und Erhitzen auf 200grad;
With lithium aluminium tetrahydride; aluminium trichloride In tetrahydrofuran; diethyl ether for 2h; Heating; Yield given;

4-chloro-1-methylpiperidine (5570-77-4) + dibenzosuberenon (2222-33-5) → 5-(1-methyl-4-piperidyl)-5H-dibenzocyclohepten-5-ol (3967-32-6)

Conditions	Yield
Stage #1: 4-chloro-1-methylpiperidine With iodine; magnesium In tetrahydrofuran for 5h; Reflux; Inert atmosphere; Stage #2: With (trimethylsilyl)methylmagnesium chloride; lithium chloride; zinc(II) chloride In tetrahydrofuran; diethyl ether at 20℃; for 0.75h; Inert atmosphere; Stage #3: dibenzosuberenon In tetrahydrofuran; diethyl ether at 0℃; for 2h; Inert atmosphere;	99%
Stage #1: 4-chloro-1-methylpiperidine With magnesium In tetrahydrofuran at 60 - 65℃; for 1h; Inert atmosphere; Large scale; Stage #2: dibenzosuberenon In tetrahydrofuran at 5 - 20℃; for 1h; Temperature; Inert atmosphere; Large scale;

sodium carbonate (497-19-8) + dibenzosuberenon (2222-33-5) → benzophenone-2,2'-dicarboxylic acid (573-32-0)

Conditions	Yield
With hydrogenchloride; potassium permanganate In water; acetone at 20℃; for 24h;	99%

dibenzosuberenon (2222-33-5) → 5H-dibenzo[a,d]cyclohepten-5-ol (10354-00-4)

Conditions	Yield
With sodium hydroxide; sodium tetrahydroborate In methanol; water	98%
With sodium borohydrid In diethyl ether; water	98%
With sodium borohydrid In diethyl ether; water	98%

dibenzosuberenon (2222-33-5) → dibenzocyclohepten-5-imine (76858-21-4)

Conditions	Yield
With 1,1,1,3,3,3-hexamethyl-disilazane; scandium tris(trifluoromethanesulfonate) In chlorobenzene at 90℃; for 12h; Inert atmosphere;	98%
With ammonia; titanium tetrachloride In toluene at 25℃; for 16h;	93%
With ammonia; titanium tetrachloride In toluene at 0 - 25℃; for 12.25h;	80.4%
With ammonia; titanium tetrachloride In toluene at 25℃; overnight;	20.6 g
With ammonia; titanium tetrachloride In toluene

bromobenzene (108-86-1) + dibenzosuberenon (2222-33-5) → 5-phenyl-5H-dibenzocyclohepten-5-ol (55090-29-4)

Conditions	Yield
Stage #1: bromobenzene With magnesium In tetrahydrofuran for 0.333333h; Stage #2: dibenzosuberenon In tetrahydrofuran for 0.5h; Heating;	97%
With magnesium 1) Et2O, 2) Et2O, 2a) reflux, 2 h, 2b) r. t., 2 h; Yield given. Multistep reaction;

methylmagnesium bromide (75-16-1) + dibenzosuberenon (2222-33-5) → 5-hydroxy-5-methyl-5H-dibenzocycloheptene (18259-45-5)

Conditions	Yield
In tetrahydrofuran; diethyl ether Ambient temperature;	97%
In tetrahydrofuran; diethyl ether at 15 - 20℃; for 2h;	83%
In diethyl ether for 1h; Heating;	71%

2-(phenylethynyl)phenylacetylene (143192-60-3) + dibenzosuberenon (2222-33-5) → 5-[[2-(phenylethynyl)phenyl]ethynyl]-5H-dibenzo[a,d]cyclohepten-5-ol (372967-65-2)

Conditions	Yield
With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 2.5h;	97%

2-Bromobiphenyl (2052-07-5) + dibenzosuberenon (2222-33-5) → spiro-fluorene-dibenzosuberene (121472-88-6)

Conditions	Yield
Stage #1: 2-Bromobiphenyl; dibenzosuberenon With n-butyllithium In tetrahydrofuran at -78 - 20℃; Stage #2: With hydrogenchloride; acetic acid In water for 0.333333h; Heating;	97%
Stage #1: 2-Bromobiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: dibenzosuberenon In tetrahydrofuran; hexane for 6h; Stage #3: With hydrogenchloride; acetic acid In water for 12h; Reflux;	94%
Stage #1: 2-Bromobiphenyl; dibenzosuberenon With tert.-butyl lithium In tetrahydrofuran; hexane at -78℃; for 6.5h; Stage #2: With hydrogenchloride; acetic acid In water for 12h; Reflux;	94%
Stage #1: 2-Bromobiphenyl In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: dibenzosuberenon In tetrahydrofuran; hexane for 6h; Stage #3: With hydrogenchloride; acetic acid In water for 12h; Reflux;	94%

tris(trimethylsilyl)silyllithium (4110-02-5) + dibenzosuberenon (2222-33-5) → 8-bis(trimethylsilyl)-5(5-hydroxy-dibenzo[a,d]cyclohepten-5-yl)-1-trimethylsiloxy-4,5-dihydro-dibenzo[a,d]-8-silabicyclo[3,2,1]octane

Conditions	Yield
In 1,2-dimethoxyethane -78 deg C to rt;	96%

3,6-di(2'-pyridyl)-1,2,4,5-tetrazine (1671-87-0) + dibenzosuberenon (2222-33-5) → 1,4-di(pyridin-2-yl)-2,4a-dihydro-9H-dibenzo[3,4:6,7]cyclohepta[1,2-d]pyridazin-9-one

Conditions	Yield
In toluene at 120℃; for 10h; Diels-Alder Cycloaddition; Sealed tube;	96%
In toluene at 120℃; for 20h; Diels-Alder Cycloaddition;	94%

3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine (57654-36-1) + dibenzosuberenon (2222-33-5) → 1,4-di(pyridin-4-yl)-2,4a-dihydro-9H-dibenzo[3,4:6,7]cyclohepta[1,2-d]pyridazin-9-one

Conditions	Yield
In toluene at 125℃; for 16h; Diels-Alder Cycloaddition; Sealed tube;	96%

dibenzosuberenon (2222-33-5) → trans-10,11-dibromo-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (39654-52-9)

Conditions	Yield
With bromine In tetrachloromethane	95%
With bromine In tetrachloromethane for 1.5h;	90%
With bromine In chloroform at 0 - 20℃; Inert atmosphere;	74%

dibenzosuberenon (2222-33-5) → 10,11-dibromo[(10,11-dihydro-5H-dibenzo[a,d]cyclohept-5-one)] (57295-97-3)

Conditions	Yield
With bromine In tetrachloromethane for 5.25h;	95%
With bromine In tetrachloromethane at 20℃; for 1.5h;	92%
With bromine In tetrachloromethane at 20℃; for 1.5h;	92%
With bromine In acetic acid

dibenzosuberenon (2222-33-5) → N-methyl-5H-dibenzocyclohepten-5-imine (59864-52-7)

Conditions	Yield
With methylamine; titanium tetrachloride In benzene	95%

dibenzosuberenon (2222-33-5) + allylmagnesium bromide (1730-25-2) → 5-Allyl-dibenzo-cyclohepten-5-ol (16203-85-3)

Conditions	Yield
In tetrahydrofuran at 20℃; for 2h; Inert atmosphere;	95%

dibenzosuberenon (2222-33-5) → [15N]-5H-dibenzo[a,d]cyclohepten-5-one oxime

Conditions	Yield
With pyridine; [15N]hydroxylamine hydrochloride for 16h; Reflux;	95%

1,2,4,5-tetrazine-3,6-dicarboxylic acid dimethyl ester (2166-14-5) + dibenzosuberenon (2222-33-5) → dimethyl-9-oxo-4a,9-dihydro-2H-dibenzo[3,4:6,7]cyclohepta[1,2-d]pyridazin-1,4-dicarboxylate

Conditions	Yield
In toluene at 120℃; for 8h; Diels-Alder Cycloaddition;	95%
In toluene at 100℃; for 10h; Diels-Alder Cycloaddition; Sealed tube;	95%

1,2,4,5-tetrazine-3,6-dicarboxamide (36743-38-1) + dibenzosuberenon (2222-33-5) → 9-oxo-4a,9-dihydro-2H-dibenzo[3,4:6,7]cyclohepta[1,2-d]pyridazine-1,4-dicarboxamide

Conditions	Yield
In neat (no solvent) at 100℃; for 16h; Diels-Alder Cycloaddition; Sealed tube;	95%

dibenzosuberenon (2222-33-5) → 5H-dibenzocyclohepten-5-one hydrazone (61047-37-8)

Conditions	Yield
With hydrazine hydrochloride; hydrazine hydrate In various solvent(s) Heating;	94%
Multi-step reaction with 2 steps 1: Lawessons reagent / benzene / 24 h / Reflux 2: hydrazine hydrate / benzene; ethanol / 2 h / Reflux View Scheme

isopropylmagnesium bromide (920-39-8) + dibenzosuberenon (2222-33-5) → 5H-dibenzo[a,d]cyclohepten-5-ol (10354-00-4) + 5-isopropyl-5H-dibenzo[a,d]cyclohepten-5-ol (123299-71-8)

Conditions	Yield
Stage #1: isopropylmagnesium bromide With (trimethylsilyl)methylmagnesium chloride; lithium chloride; zinc(II) chloride In tetrahydrofuran; diethyl ether at 20℃; Grignard addition; Stage #2: dibenzosuberenon In tetrahydrofuran; diethyl ether at 0℃; for 3h; Grignard addition;	A 6% B 94%
Stage #1: isopropylmagnesium bromide With (trimethylsilyl)methylmagnesium chloride; lithium chloride; zinc(II) chloride In tetrahydrofuran; diethyl ether at 20℃; for 0.75h; Inert atmosphere; Stage #2: dibenzosuberenon In tetrahydrofuran; diethyl ether at 0℃; for 3h; Inert atmosphere;	A 6% B 94%
In tetrahydrofuran at 0℃; Grignard addition;	A 89% B 11%

diethyl isocyanomethylphosphonate (41003-94-5) + dibenzosuberenon (2222-33-5) → 5-(isocyanomethylen)-5H-dibenzo[a,d]cycloheptene

Conditions	Yield
Stage #1: diethyl isocyanomethylphosphonate With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Horner-Wadsworth-Emmons Olefination; Stage #2: dibenzosuberenon In tetrahydrofuran for 16h; Horner-Wadsworth-Emmons Olefination;	94%

Upstream product

• 256-81-5 suberene 
• 1210-35-1 10,11-Dihydro-5H-dibenzo[a,d]cyclohepten-5-one 
• 67-56-1 methanol 
• 6141-56-6 5-diazo-5H-dibenzocycloheptene 
• 109217-78-9 C₁₅H₁₀N₂⁽¹⁺⁾ 
• 39654-52-9 trans-10,11-dibromo-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one 
• 101023-29-4 5-(3,3-diphenyl-2,3-dihydro-2-oxoindol-1-yl)dibenzocyclohepten-1-yl diphenylethanoate 
• 833-48-7 dibenzosuberane 
• 4444-44-4 1a,10b-dihydro-6H-dibenzo[3,4:6,7]cyclohepta[1,2-b]oxiren-6-one 
• 36795-27-4 diphenylethane-2-carboxylic acid chloride 
• 59436-15-6 5-bromodibenzosuberene 
• 16203-85-3 5-Allyl-dibenzo-cyclohepten-5-ol 
• 35066-77-4 5-<(5H-dibenzocyclohepten-5-yl)oxy>-5H-dibenzocycloheptene 
• 1210-34-0 dibenzosuberol 

Downstream Products

• 303-53-7 Cyclobenzaprine 
• 256-81-5 suberene 
• 372967-65-2 5-[[2-(phenylethynyl)phenyl]ethynyl]-5H-dibenzo[a,d]cyclohepten-5-ol 
• 4517-99-1 Wy 41770 
• 1007090-75-6 N-(4-nitrophenyl)-10,11-dihydro-10,11aza-cyclopropa-5H-dibenzo[a,d]cyclohepten-5-one 
• 1044252-68-7 5-hydroxy-5-(8-methoxy-1-naphthyl)-5H-dibenzo[a,d]cycloheptene 
• 2216-69-5 1-Methoxynaphthalene 
• 1192749-51-1 5-(α,α,α-trifluorotolyl)ethynyl-5H-dibenzo[a,d]cyclohepten-5-ol 
• 3967-32-6 5-(1-methyl-4-piperidyl)-5H-dibenzocyclohepten-5-ol 
• 10354-00-4 5H-dibenzo[a,d]cyclohepten-5-ol 
• 1971-54-6 5-ethyl-5-hydroxy-5H-dibenzo[a,d]cycloheptene 
• 260416-00-0 5-cyclohexyl-5H-dibenzo[a,d]cyclohepten-5-ol 
• 127903-33-7 C₂₂H₁₈O 
• 27980-44-5 5-benzylidene-5H-dibenzo[a,d]cycloheptene 

Relevant articles and documents

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Substituted 9-Anthraldehydes from Dibenzocycloheptanol Epoxides via Acid-Catalyzed Epoxide Opening/Semipinacol Rearrangement

Starting from benzaldehyde derivatives, the corresponding dibenzocycloheptenol could be prepared in five steps. Under both substrate (secondary vs tertiary alcohol and the substituents on the aromatic ring(s)) and condition control, the subsequent epoxidation and acid-catalyzed epoxide opening/semipinacol rearrangement/aromatization afforded the corresponding 9-anthraldehydes in good yields, up to 88% over two steps. The presence of the electron-withdrawing group(s) on the aromatic ring(s) suppressed the rate of the epoxidation while the subsequent semipinacol rearrangement step required heating; the presence of the electron-donating group(s), on the other hand, frequently led to the decomposition during the epoxidation. From the mechanistic studies, the semipinacol rearrangement of the epoxide could precede the ionization at the bisbenzylic position, yielding the aldehyde intermediate. The ensuing dehydrative aromatization led to the formation of 9-anthraldehyde. Conversely, nucleophilic addition to the aldehyde and dehydrative aromatization with concomitant loss of formic acid led to anthracene.

BROMINE FREE PREPARATION OF 5H-DIBENZO [A,D] CYCLOHEPTEN-5-ONE

The invention relates to a convenient procedure for the preparation of 5H- Dibenzo[a,d] cyclohepten-5-one in high yield an purity from 10,11-Dihydro-5H-dibenzo[a,d]cyclohepten-5-one. The procedure is not only convenient to be adopted on an industrial scale but also safe and environment friendly.